Polyethylenimine shampoo compositions

ABSTRACT

CLEAR, VISCOUS, HOMOGENEOUS SHAMPOO COMPOSITIONS WHICH HAVE EXCELLENT CONDITIONING CHARACTERISTICS ARE EFFECTIVE AGAINST PITYROSPORUM OVALE CONTAINING AS THE ACTIVE INGREDIENTS A DETERGENT SELECTED FROM THE GROUP CONSISTING OF BETAINES, SULFOBETAINES, AMINE OXIDES, AND MIXTURES THEREOF, A WATER-SOLUBLE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYETHYLENIMINES, ETHOXYLATED POLYETHYLENIMINES, AND PROPOXYLATED POLYETHYLENIMINES HAVING A MOLECULAR WEIGHT FROM ABOUT 1,800 TO ABOUT 500,000, AND AN AQUEOUS VEHICLE.

United States Patent 3,769,398 POLYETHYLENIMINE SHAMPOO COMPOSITIONSGordon Trent Hewitt, Upper Montclair, N.J., assignor toColgate-Palmolive Company, New York, NY. No Drawing. Filed May 25, 1970,Ser. No. 40,385

Int. Cl. A61k 7/06 US. Cl. 424-70 8 Claims ABSTRACT OF THE DISCLOSUREThis invention relates to clear, viscous, homogeneous shampoocompositions which have outstanding hair conditioning characteristicsand are effective against Pityrosporum ovale. The instant shampoocompositions have all of the basic characteristics of commerciallyacceptable shampoos-they clean but maintain hair luster, are clear,viscous, and homogeneous, condition hair and leave it easy to manage (nostatic flyaway or tangles), and form copious, lather even in hard water.

The inventive compositions are also suitable for cleaning andconditioning the human hair which is used to make hairpieces such asWigs and toupees. It is considered that the hair in such hairpiecesshould be free of the P. ovale yeast in order to eliminate or minimizethe problems associated with migration of such yeast to the scalp of thehairpiece wearer. Since the described compositions efiectively inhibitthe growth of P. ovale, they are particularly suitable for cleaning thehair prior to or after its fabrication into hairpieces.

It is, therefore, an object of this invention to provide clear, stable,homogeneous shampoo compositions which have excellent hair conditioningcharacteristics, and inhibit the growth of P. ovale.

In general the preferred compositions of this invention are comprised offrom about to about 25 percent by weight of a betaine, sulfobetaine, oramine oxide detergent, and mixtures thereof, from about 0.1 to about 3.0percent by weight of a water-soluble polyethylenimine (PEI), and anaqueous medium and minor ingredients to make the balance of thecomposition. Ad ditionally, an imidazoline or oxazoline foam booster maybe added in an amount of from about 1.0 to about 6.0 percent by weightof the total composition.

The pH of the composition ranges from about 5.0 to about 9.0 but ispreferably adjusted to the near neutral range of 6.5 to 8.0. A lower pHwill help solubilize the imidazoline or oxazoline foam booster andenhance their cationic nature; however, too low a pH means that freefatty acids in the natural hair oils will be more tenacious and not asreadily removed by the surfactant. A pH of about 7.5 is most preferred.

Patented Oct. 30, 1973 ice It has been found that PEI in a free anduncomplexed form is an outstandingly good antimicrobial agent havingboth inhibitory activity against P. ovale (MIC of 3.9 ,ug./ml.) andsubstantivity to the hair and scalp. PEI, however, is a cationicpolyamine and has been found to complex strongly with the usualanionic-acting shampoo surfactants, including amphoterics at theiruseful alkaline pH values and soaps. When PEI is present in a shampooalong with an anionic-acting surfactant, the PEI loses its antimicrobialcharacteristics; the complex of PEI with the anionic surfactant seems todestroy this extremely valuable property. However, PEI can be formulatedinto a superior shampoo composition and still maintain its valuableantimicrobial characteristics provided that the shampoo compositionscontain carefully selected groups of detergents which do not complexwith PEI and which themselves exhibit some inhibitory activity toward P.ovale. The useful detergents are the zwitterionic detergents such as thebetaines and sulfobetaines and the semi-polar amine oxide detergents. Insuch non-anionic compositions the PEI is uncomplexed and thus free toact as an antimicrobial agent.

Moreover, as was stated previously, all of the ingredients in theseshampoos were chosen on the basis of their own distinct inhibitoryaction toward P. ovale. Myristyl and palmityl betaine both have MICsagainst P. ovale of about 250 ng./ml., lauryl betaine of about 500,ugJmL, l-hydroxyethyl-Z-coco imidazoline of about 250 ,ug./ml., andlauryl dimethyl amine oXide of about 1250 ,ugjml. Thus all of the activeingredients in the shampoo are effective to a greater or lesser degreeagainst P. ovale.

In order to determine the substantivity of PEI on the hair the RubineDye Test is used. In this test a 0.5-percent aqueous solution of DirectFast Rubine WS dye is adjusted to a pH of 3.5 with acetic acid. Thenapproximately 0.5 gram of white hair (or wool) is immersed or rubbed (toproduce a lather) for 3 minutes in a shampoo solution. The shampooconcentration is approximately 10 parts shampoo to parts water at roomtemperature to simulate hair shampooing. After thorough rinsing withwater the damp hair sample is immersed for 5 minutes in the dye solutionat F. The hair is then rinsed thoroughly with room temperature water.The presence of a deep red color indicates that the hair or wool hasdeposited on its some cationic active substance. In the absence of suchan absorbed cationic, the hair color is essentially unchanged, that is,there is no takeup of the Rubine dye.

It was found that the deposits from the instant nonanionic shampoosolutions formed a very strong, very difiicult to remove attachment ofRubine dye indicating excellent substantivity of PEI. PEI, per se, doesnot deposit from shampoo solutions containing anionics, such as laurylsulfates and fatty alcohol ether sulfates.

The PEI polymers which can be used in the shampoos of this invention canbe prepared by polymerizing ethyl- In a standard laboratory test todetermine antimicrobial activity PEI offered almost no generalantimicrobial properties as it was ineffective against S. aureus (MICgreater than 500 1.g./Inl.), Str. mitts (MIC greater than 500 ag./ml.),E. 001% (MIC greater than 1000 ag/1111.), Ps. aerugmosa (MIC greaterthan 1000 ,ug./ml.), 0. albt'cans (MIC of 1000 ,ug./ml.), and A. mger(MIC greater than 1000 ng./ml.). Against T. 'ggettagt/"oplhptes PEI wasvery modestly inhibitory (MIC of 2 Minimum Inhibitory Concentration(MIC) of an individual substance or formulation needed to inhibit thegrowth of a particular organism.

enimine in the presence of a catalyst such as carbon dioxide, sodiumbisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, aceticacid, etc. Specific methods of preparation are described in US. Pats.Nos. 2,182,306, Ulrich et al., granted Dec. 5, 1939; 3,033,746, Moyle etal., granted May 8, 1962; 2,208,095, Esselmann et al., granted July 16,1940; 2,806,839, Crowther, granted Sept. 17, 1957; and 2,553,969,Wilson, granted May 21, 1951.

Similarly, alkoxylated PEIs can be prepared, for example, by reactingone part by weight ethylene oxide or propylene oxide with one part byweight PEI prepared as described above and having a molecular weightgreater than about 1,800. Preferably, the weight ratio of PEI toalkylene oxide is at least about 1:1, but ratios as low as about 1:4 areacceptable.

It is believed that the general structure of the PEI polymer is:

wherein x represents a whole number of suflicient magnitude to yield apolymer of molecular weight greater than about 1800. Generally, x mayvary from 14 to about 1500, and preferably x is from 45 to 5,000. Branchchains occur along the polymeric backbone and the relative proportionsof primary, secondary, and tertiary amino groups present in the polymerwill vary, depending onthe manner of preparation. The distribution ofamino groups in a typical PEI is approximately as follows:

The polymers suitable for use in this invention have viscosities (in 1percent by weight aqueous solutions) ranging from about 1.0 to about 3.0centipoises (absolute viscosity) when measured by an Ostwald viscometerat 100 F. The molecular weight of the PEI polymers includes the entirerange of dermatologically-safe materials. The preferred polymers have anaverage molecular weight within the range of about 1800 to about 200,000with the most preferred polymer having an average molecular weight ofabout 100,000. The molecular weight may range as high as 500,000 forethoxylated and propoxylated polymers.

The useful zwitterionic detergents are betaines and sulfobetaines havingthe following general formula:

1'1. where R, is an alkyl group having 10 to about 20 carbon atoms,preferably 12 to 16 carbon atoms, R and R are each alkyl groups having 1to 3 carbon atoms, R is an alkylene or hydroxyalkylene group having from1 to 4 carbon atoms, and X is an anion selected from the groupconsisting of S and COO=. The preferred betaines and sulfobetaines havethe following formulas:

where R in each formula is an alkyl group having about to about carbonatoms.

Amido betaines and amido sulfobetaines having the following structuremay also be used:

where R in both formulas is an alkyl group having about 10 to about 20carbon atoms.

The preferred compound from the group of zwitterionic detergents is coco3 dimethyl betaine.

The useful semi-polar amine oxide detergents have the following generalformula:

Amine oxide R R R N 0 where R is an alkyl, alkenyl, or monohydroxyalkylgroup having 10 to about 20 carbon atoms, and R and R are each selectedfrom the group consisting of methyl, ethyl, propyl, ethanol, andpropanol groups.

The preferred amine oxide detergent is myristyl dimethyl amine oxide.

The useful foam boosters are the imidazoline and oxazoline materialshaving the following general formulas:

Oxazoline where R is an alkyl group having about 9 to about 17 carbonatoms, and R and R are selected from the group consisting of hydrogenand alkyl and hydroxyalkyl groups containing from 1 to 2 carbon atoms.

Imidazoline oH,-om

where R is an alkyl group having about 9 to about 17 carbon atoms, and Ris selected from the group consisting of hydroxy methyl, hydroxyethyl,hydroxypropyl and CH CH OCH CH OH.

In the preparation of the imidazoline and oxazoline foam booster, thecarboxyl carbon of the fatty acid reactant becomes part of the ring, andthus the resultant alkyl group contains one less carbon than thecorresponding fatty acid.

The preferred imidazoline foam booster is l-hydroxyethyl-2-cocoimidazoline; the preferred Oxazoline foam booster is 2-coco-4,4dihydroxymethyl oxazoline.

A Water-soluble, nonionic synthetic detergent may be substituted for thepreferred zwitterionic and amine oxide detergents; however, theresultant shampoo compositions are non-preferred due to the lowerfoaming properties of the nonionic detergents. Suitable nonionicsynthetic organic detergents are generally the condensation product ofan organic aliphatic or alkyl aromatic hydrophobic compound andhydrophilic ethylene oxide groups or the polyhydration product thereof,i.e., polyethylene glycol.

The term coco as used herein refers to the mixture of alkyl groups foundin the alcohols obtained by hydrogenating the mixture of fatty acidsobtained upon hydrolysis of coconut oil, that is, Cs8%; Clo-7%; Cue-48%;C1i17%; C1e-15% and Cur-5%.

Practically any hydrophobic compound having a carboxy, hydroxy, amido,or amino group with a free hydrogen attached to the nitrogen can becondensed with ethylene oxide to form a nonionic detergent. Suitablenonionic detergents include the polyethylene oxide condensate of onemole of alkyl phenol containing from about 6 to about 12 carbon atoms ina straight or branched chain configuration with about 5 to 30 moles ofethylene oxide, e.g., nonyl phenol condensed with 9 moles of ethyleneoxide; the condensation product of a higher alcohol containing about 8to 22 carbon atoms in a straight or branched chain configuration withabout 5 to 30 moles of ethylene oxide, e.g., lauryl-myristyl alcoholcondensed with 16 moles of ethylene oxide; the condensation product ofethylene oxide on a hydrophobic base formed by the condensation ofpropylene oxide on propylene glycol wherein the molecular weight of thehydrophobe ranges from about 1,500 to 1,800 and the polyethylene oxidecontent may comprise up to 50% of the total weight of the condensate;and the ethylene oxide addends of monoesters of hexahydric alcohols andinner ethers thereof with higher fatty acids containing about to 20carbon atoms,

e.g., sorbitan monolaurate, sorbitan mono-oleate, and mannitanmonopalmitate. Alternatively, such nonionic detergents may be used inaddition to the preferred betaine, sulfobetaine, and amine oxidedetergents in concentrations of about 3% to 10% by weight of the shampoocomposition.

The aqueous vehicle may contain an organic solvent such as monohydricand dihydric alcohols containing 2 to 3 carbon atoms. The solvent may bepresent in an amount of from about 5 to 30 percent by weight andpreferably from about 10 to 20 percent.

In the most preferred shampoo compositions, the betaine, sulfobetaine,and amine oxide detergents are present in an amount of 10% to about 20%by weight; the PEI is present in an amount of about 1% to 2% by weight;the imidazoline and oxazoline foam booster is present in an amount ofabout 3% to 5% by weight; and the aqueous medium or vehicle is thebalance. When a mixture of detergents is used, the preferredconcentration of the individual detergents is reduced because the totalamount of detergent present in the most preferred compositions rangesfrom about 10% to about 20% by weight.

Various conventional shampoo additives may also be present, for example,compatible nonionic thickeners, perfumes, pH adjusters, sequesteringagents, opacifiers, compatible antimicrobial compounds, etc. Suchadditives are present in their conventional amounts ranging from about0.4 to about 10 percent by weight. More specifically, coconut monoordiethanolamides and strongly ionizing salts such as sodium chloride andsodium sulfate may be used up to about 5 percent of the formula weight.These compounds serve to aid in the compatibilization of thepolymer-detergent composition; however, they are not essential.

EXAMPLE I Shampoo compositions were prepared having the followingcomposition:

EXAMPLE I Coco dimethylbetalneh 10. 0 1o. 0 10. o Myristyl dimethylamine oxide 5. 0 l-hydroxyethyl-2-coco imidazoline 5.02-coeo-4,4-dihydroxymethyl oxazoline 6. 0 Polyethylenimine (M.W.50,000)-.. 1. 0 1. 0 1. 0 HCl (pH adjustment to about 7.5). 1. 0 1. 0 1.0 Propylene glycol 5. 0 5. 0 Perfume 0. 4 0. 4 0. 4 Deionized water 1Balance.

These compositions were clear, stable liquids which yielded copiouslather, left hair free from tangles and static flayaway, and showedinhibitory action against the growth of P. ovale.

EXAMPLE II Coco dimethyl sulfobetaine 10.0 l-hydroxyethyl-Z-cocoimidazoline 5.0 Polyethylenimine (M.W. 1800) 2.0 HCl (to adjust pH toabout 7.5) 1.0 Deionized water Balance EXAMPLE III Myristyl dimethylbetaine 15.0 l-hydroxyethyl-Z-coco imidazoline 2.0 Polyethylenimine(M.W. 100,000) 1.0 HCl (to adjust pH to about 7.5 1.0 Ethanol 10.0Deionized water Balance EXAMPLE IV Palmityl dimethyl amido betaine 15.0Polyethylenimine (M.W. 50,000) 2.0 HCl (to adjust pH to about 7.5 1.0NaCl 3.0 Deionized water Balance EXAMPLE V Myristyl dimethyl amine oxide10.0 Polyethylenimine (M.W. 1800) 3.0 HCl (pH adjustment to about 7.5)1.0 Perfume 0.4 Deionized water Balance In order to determine theconditioning efiect of PEI on the hair the following test was conducted.

Clean hair samples (washed in a nonionic surfactant and rinsed indistilled water and in ethanol) were dipped in a 2-percent oleicacid-alcohol solution to provide free fatty acid such as is present onthe scalp. After drying the various tresses were shampooed with:

(A) Composition A of Example I (B) Composition A with PEI omitted (C)Shampoo containing 19% triethanolarnine lauryl sulfate and 5%lauryl-myristyl diethanolamide in an aqueous medium.

The shampoo solutions were diluted with water to 10 parts shampoo toparts water to simulate dilution in actual shampooing. The shampooedtresses were rinsed well and dried. As a control tress one of the cleantresses was not treated with oleic acid but was washed with CompositionA of Example I.

The results of this test revealed that the tress which had oleic acid onit and washed with Composition A of Example I was low in friction duringdry combing, was low in static fly when combed, and felt smooth.However, the tress having-no oleic acid present which was shampooed withComposition A of Example I was difficult to comb and gave static fly.Further, Composition A without PEI also was difiicult to comb and gavestatic fly. These results indicate that the conditioning effects ofComposition A of Example I are probably due to the fact that PEIdeposits on the hair and also redeposits the natural oils. Composition Aalso gave superior conditioning results as compared to the conventionalanionic/alkanolamide shampoo whose washed tress also gave static fly andwas difficult to comb.

Percentage values employed in the specification and claims refer topercent by weight of the total composition unless otherwise stated.

What is claimed is:

1. A clear, homogeneous shampoo composition particularly suitable forconditioning hair and for inhibiting the growth of Pityrosporum ovalewhich consists essentially of about 5 to 25 percent by weight of awater-soluble detergent selected from the group consisting of betainesand sulfobetaines having the formula wherein R is alkyl of 10 to 20carbons, R and R are each alkyl of 1 to 3 carbons, R is alkylene orhydroxyalkylene of 1 to 4 carbons, and X is S or CO C-alkyl betaines ofthe formula wherein R is an alkyl of to carbons, C-alkyl sultaines ofthe formula wherein R is an alkyl of 10 to 20 carbons, amine oxides ofthe formula R R R N O wherein R is an alkyl, alkenyl, ormonohydroxyalkyl of 10 to 20 carbons, and R and R are each methyl,ethyl, propyl, ethanol, or propanol, and mixtures of the foregoingdetergents; 0.1 to 3 percent by weight of a water-soluble polymerselected from the group consisting of polyethylenimine having amolecular weight from about 1,800 to about 200,000 and the reactionproduct of said polyethylenimine with either ethylene oxide or propyleneoxide in a weight ratio of polyethylenimine to alkylene oxide of atleast 1:4, said reaction product having a molecular weight of up to500,000, said polymer exhibiting inhibitory activity againstPityrosporum ovale; and an aqueous vehicle, said composition being freeof anionic-acting surfactants.

2. The shampoo composition as set forth in claim 1 wherein saiddetergent is a mixture of said betaine or sulfobetaine corresponding tothe formula and said amine oxide and said mixture is present in anamount of 10 to 20 percent by weight of the composition.

3. The shampoo composition as set forth in claim 1 wherein saiddetergent is said amine oxide.

4. The shampoo composition as set forth in claim 1 wherein said aqueousvehicle contains from about 10 to 20 percent by weight of the totalcomposition of an organic solvent selected from the group consisting ofmonohydric and dihydric alcohols containing 2 to 3 carbons.

5. The shampoo composition as set forth in claim 1 wherein said aqueousmedium is water.

6. The shampoo composition as set forth in claim 1 wherein said polymeris said polyethylenimine having a molecular weight of about 1,800 to100,000.

7. The shampoo composition as set forth in claim 1 wherein saiddetergent is said betaine or sulfobetaine corresponding to the formula8. The shampoo composition'as set forth in claim 1 which contains inaddition from about 1 to 6 percent by weight of the total composition offoam boosting compound selected from the group consisting of anoxazoline having the following structure wherein R is alkyl containing 9to 17 carbons and R and R are each selected from the group consisting ofhydrogen, alkyl containing 1 to 2 carbons, and hydroxyal'kyl containingfrom 1 to 2 carbons and an imidazoline having the following structurewherein R is alkyl containing 9 to 17 carbons and R is selected from thegroup consisting of hydroxymethyl, hydroxyethyl, hydroxypropyl, and CHCH OCH CH OH.

References Cited UNITED STATES PATENTS 3,033,746 5/ 1962 Moyle et a1.424-325 3,098,794 7/ 1963 Dohr et al. 424 X 3,206,512 9/1965 Koebner eta1. 424325 X 3,280,179 10/1966 Ernst 42470 X 3,449,430 6/1969 Dohr etal. 42470 X 3,470,102 9/1969 Heinz 42470 X FOREIGN PATENTS 451,4125/1968 Switzerland 424316 1,111,708 5/1968 Great Britain 4243251,078,075 8/ 1967 Great Britain.

OTHER REFERENCES Wells et al., Cosmetics and The Skin, p. 404, ReinholdPublishing Corp. New York, 1964.

American Perfumer and Cosmetics, vol. 84, pp. 37- 39, December 1969.

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US.Cl. X.R.

252106; 424DIG. 24, 78, 316, 325

